Ether-carbonates and polymers



Patented June 6, 1950 Henry A. Pace, Akron,

Corporation, Akron,

Delaware Ohio, assignor to Wingfoot Ohio, a corporation of No Drawing. Application June 15, 1946, Serial No. 677,118

1 This invention relates to ether-carbonates of organichydrates, to-their method of formation and to their polymers.

It is well-known that it is extremely difiicult to prepare organic compounds having two hydroxyl groups attached to the same carbon atom. Such c'ompoundsare referred to as being hydrates and are generally prepared from the corresponding carbonyl compound, particularly the aldehyde. Ordinarily, these hydrates are unstable and in water solution are believed to exist in equilibrium with their aldehydes or ketones. It has been discovered that a hydrate may be treated in such a way as to'form a highly stable compound having both an ether group and a carbonate group attached to the same carbon atom. It has also been discovered that this same type of ethercarbonate compound may be prepared starting with an aldehyde or hemiacetal. However, in each case it is necessary that the carbon atom alpha to the carbon atom carrying the twohydroxyl groups, in the case of the hydrate, or the aldehyde group in the case of the aldehyde, or alpha to the carbon atom carrying both the ether group and the hydroxyl group in the case of the hemiacetal x H v a s-temp Z R1 carry at least three electro-negative groups.

The ether-carbonates of this invention have the general formula x H ing hydrate containing halogen is 'chloralhy- (irate, CC1sCH(OI-I) 2.

Another electro-negative group is one containing a secondary carbon atom and is represented by-general formula in which A is an electro-negative group. Thus, the electro-negativity of the group 12 Claims. (o1. 260-475) 2 is established through the group represented by A, such as halogen including chlorine and bromine. ;An example of a corresponding hydrate containing an electro-negative group of this type is 2,2,3-trichlorobutyral hydrate CH3CH CD C (CD zCI-IKOH) 2 (butyrchloral). An aldehyde containing this secondary carbon negative group is 2,2,3-trichlorobutyraldehyde,

' onsonrcnownzono Another electro-negative group is one containing a'primary carbon atom and is represented bythe general formula which are used as one of the starting materials in the'preparation'of the ether-carbonates off this invention, comprises treatment of an aldehydehaving the general formula gilt a;

with water at any convenient temperature, e. g., room temperature, and evaporating to remove the water and recover the hydrate. Known hydrates that may be used in the preparation of these ether-carbonates are trichloroacetaldehyde hydrate and 2,2,3 -trichlorobutyraldehyde hydrate. J A general method for the preparation of alde-,:

hydes having the general formula Yiia which' may also be as a starting materialini the preparation of the ether-carbonates of this invention, comprises the chlorination of ethanol or acetaldehydes; the hydrochlorination, followed by chlorination, of crotonaldehyde and the chlorination of paraldehyde, using the conditions well-known with these methods. Known aldehydes that may be used in this invention are trichloroacetaldehyde and 2,2,3-trichlorobutyraldehyde.

When using the hydrate as a starting material,

it has been discovered that the desired ether-carbonate of this invention may be prepared by re acting the hydrate with a halo-iormate havin the general formula agents operate to take up the hydrogen halide as it is iormed, in a vessel and cool the mixture to about C. The formate is then added slowly with constant stirring while maintaining the temperature of the mixture between about 0 C. and about 10 C. The apparatus should be equipped with means for relieving the reaction zone of carbon dioxide which is generated during the reaction. For each mol of hydrate being reacted, a slight excess of iormate over the two mols required should be used, together with about two mols oi the neutraiizmg agent. After the reaction is complete, which may take between about 2 hours and about 12 hours, depending upon the conditions of the reaction, the resulting mixture is worked up by diluting with water containing a small amount of hydrochloric acid to remove the pyridine hydrochloride and excess pyridine, washing twice with water, drying with calcium chloride and then recovering the desired product by vacuum distillation in the presence of a polymerization inhibitor, such as copper wire. The desired ether-carbonate is a Water-white material having a very slight characteristic (musky) odor.

When using the aldehyde as the starting material, it is first reacted with an alcohol having the general formula ROH, in which R is an aliphatic radical, saturated or unsaturated, at a temperature of between about 25 C. and about 30 C. for a period of time between about 1 hour and about 5 hours to produce the corresponding etherhydrate or hemiacetal having the general formula in which X, Y, Z and R are radicals, as previously defined. This ether-hydrate is then reacted with a halo-iormate in the presence of a neutralizing agent, above defined, at a temperature between about 0 C. and about C. for a period of between about 2 hours and about 12 hours to produce the desired ether-carbonate. The following examples are illustrative but not limitativeof the present invention. Parts, where given, are by weight.

EXAMPLE 1 1-(marry-2,2,2-trichZ0rethyl-allyl carbonate A mixture was prepared comprising one mol of chloral hydrate [CC13CI-l(OI-I) z] and 2.03 mols of pyridine, and cooled to 0 C. To this mixture was added 2.17 mols of allyl chloroformate over a period of 6 hours while maintaining the reaction mixture at a temperature of 5 C.

The resulting reaction mixture was worked up by diluting with water containing .1 mol of hydrochloric acid to remove the excess pyridine and then washing again with water to remove the pyridine hydrochloride formed, drying with calcium chloride and then distilling under vacuum in the presence of 1 gram of copper wire to produce a yield of of l-alloxy-2,2,2-trichloroethylallyl carbonate having a boiling point of l17118 C. at 3 mm. The product had a very slight musky odor and was water-white. Analysis of the product showed a chlorine content of 37.1%, index of refraction, 11 1.4692, and density, 116 1.2932.

A quantity of 1-alloxy-2,2,2-trichloroethyl allyl carbonate was heated at 65 C. in the presence of 1% of benzoyl peroxide for 1'7 hours to produce a resinous mass having a Rockwell hardness of 94.

EXAMPLE 2 .I-allory-2,2,3-trichlorobutyl allyl carbonate A mixture of one mol of 2,2,3-trichlorobutyral hydrate and two mols of pyridine was cooled to 0 C. and then 2.2 mols of allyl chloroformate was added slowly for a period of 6 hours while maintaining the temperature at 5 C. The resulting mixture was worked up in accordance with the procedure set forth in Example 1 and a yield of 87% of l-alloxy-2,2,3-trichlorobutyl allyl carbonate was obtained, having a boiling point of 113-144" C. at 5 mm. The product also had an index of refraction, 11. 1.4764; and density, (in; 1.2609.

A quantity of the 1-alloxy-2,2,3-trich1orobuty1 allyl carbonate was heated at 65 C. in the presence of 1% of benzoyl peroxide for 22 hours to obtain a reaction mass having a Rockwell hardness of M 100.

EXAMPLE 3 1-aZloxy-2,2,2-trichlorethyl-allyl carbonate To 50' parts of chloral hydrate cooled to 5 C. was added 19.7 parts of allyl alcohol and the solution maintained at room temperature (75 F.) for 2 hours. A near theoretical yield of the hemiacetal chloral ailylate [CCIBCHQOH) OCsH5] was obtained having a boiling point of 1-15-1l=6 (3., density (i/16 1.3701 and an index of refraction, 12 1.4832.

To a cooled mixture of 51.4 parts of chloral allylate and 21 parts of pyridine was slowly added 50 parts of allyl chloroformate during -a period of 35 minutes while maintaining the mixture at a temperature of about 10 C. and during constant stirring. The reaction mass was then allowed to warm up to room temperature (75 F.) and agitated at this temperature for 1 hours. The resulting mass was worked up in accordance with the procedureset forth in Example 1 and a.

90% ield of the desired ,product was obtained, having a boiling point of 119 C. at 3 mm., an index of refraction, 11 1.4692 and density, (116 1.2934.

EXAMPLE 4 1 beta chloroallomy 2,2,3 trz'chlorobutylbeta chlorallyl carbonate u A mixture of 100 parts of 2,2,3-trichlorobutyral hydrate and 85 parts of pyridine was cooled to C. and then 180 parts of beta-chlorallyl chloroformate was slowly added over a hour period while maintaining the temperature of the mixture at about 0 C.-5 C. The resulting mixture was worked up in accordance with the procedure set forth in Example 1 and a yield of 85% of 1 beta chloralloxy 2,2,3 trichlorobutylbeta-chlorallyl carbonate was obtained, having a boiling point of 170-175 C. at 2 mm., an index of refraction, 11. 1.4950 and a density, (116 1.4010.

A quantity of the 1-beta-chloroalloxy-2,2,3- tricholorbutyl-beta-chlorallyl carbonate was heated at 65 C. in the presence of 1% of benzoyl peroxide for 8 hours to obtain a reaction mass having a Rockwell hardness of M 100.

EXAMPLE 5 hallway-2,212-trichloroethyl-beta-chlorallyl carbonate To a solution of 205 parts of chloral allylate [CC13CH(OH)OC3H51 prepared by reacting chlo- 1-alloxy 2,2,2-trichloroethyl-beta-chlorallyl car-- bonate having a boiling point of 137 C./4mm., an index of refraction, a 1.4812 and a density, d1s 1.3837.

A quantity of the 1-alloxy-2,2,2-trichloroethylbeta-chlorallyl carbonate was heated at 65 C. inthe, presence of 1% of benzoyl peroxide for 6 hours to obtain a reaction mass having a, Rockwell hardness of M 98.

The following compounds were also produced in accordance with the conditions set forth in Example 5: V

fl-betachloralloxy 2,2,2 -'trichl0roethy1, allyl carbonate (from chloral, beta-chlorocthyl alcohol and allyl chloroformate) having a B. P. 138/ 6 mm.; 11 1.4818 and (116 1.3815. Also l-betachloroalloxy-2,2,2-trichloroethyl -1- beta-chloroallyl carbonate (from chloral, beta-chlorallyl a1- cohol and beta-chloroallyl chloroformate) was produced having a B. P. 151 C./4 mm.; n l 1.4926 and dis 1.4569.

1 beta-chloroalloxy 2,2,3 trichlorobutyl 1- allyl carbonate (from 2,2,3-trichlorobutyraldehyde, beta-chloroallyl alcohol and allyl chloroformate) was also prepared having a B. P. 155 C./3 mm.; n 1.4833 and (11630, 1.3317.

The halo-formates that may be used in the preparation of these ether-carbonates are those having the formula 0 R-O-(J-X in which R, is an aliphatic radical, for example, allyl, methallyl, chlorallyl, e. g. beta chlorallyl, ethyl, crotyl, methyl, butyl, and vinyl. In general, these halo-formates are prepared by reacting phosgene (chloroformyl chloride) with an alcohol (ROH) above described, at room temperature with or without the aid of a catalyst and with or without the aid of heat, depending, of course, upon the particular alcohol being reacted. The use of a catalyst and heat will speed up the chemical reaction. Vinylchloroformate may be pro: duced by pyrolyzing ethylene glycol bis (chloroformate) at a temperature of 400-600 C., as more fully described in U. S. 2,377,085.

It has been discovered that resinification to a hard glass-like resinous mass occurs only with those compounds in which the ether and the carbonate groups are derivatives of allyl alcohol. For example, 1-alloxy-2,2,2-trichlorethyl allyl carbonate and 1-alloxy-2,2,3-trichlorobutyl allyl carbonate both polymerize easily to hard, clear, glass-like solids. Where the ether and the carbonate groups are derivatives of methallyl alcohol, ethyl alcohol, crotyl alcohol, etc., and where at least one of the groups contains a methylene radical, these compounds resinify [under the influence of heat and a catalyst to a highly viscous liquid or at best to a very soft gel.

The allyl type of ether-carbonate copolymerizes readily to desirable commercial resins with another polymerizable compound when using conditions of polymerization similar to those used with respect to the formation of the polymer. The beta chlorallyl ether-carbonate is especially valuable as a copolymerizing monomer. The co.- polymerization may also be accelerated by the usual catalysts, such as hydrogen peroxide, benzoyl peroxide, tetralin peroxide and lauroyl peroxide, as well as by increasing the temperature, pressure, etc. Polymerization and copolymeriza: tion may be carried out at any temperature from about 20 C. to about C. Desirable results are obtained when operating at a temperature between about 50 C. and about 70 C. As examples of polymerizable unsaturated compounds" having a terminal methylene group (CH2:C==) may be mentioned esters of acrylic acid, e. g., methyl acrylate, methyl methacrylate, ethyl acrylate, allyl acrylate, methallyl acrylate, chlorallyl acrylate, ethyl methacrylate, methyl chloracrylate, chlorallyl chloracrylate, propyl acrylate,

isopropyl acrylate, butyl acrylate, isobutyl acryl-' ate, phenyl acrylate, benzyl acrylate, aryl ethylenes, e. g., styrene, methyl styrene, chlorostyrene, tolyl ethylene, bromo tolyl ethylene; vinyl esters, e. g., vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutylate, vinyl valerate, vinyl cyclopentanoate, vinyl cyclohexanoate, vinyl benzoate, vinyl methyl benzoate; nitrile derivatives of acrylic acids, e. g., acrylonitrile, methacrylonitrile; malonic acids and their esters, e. g., methylene malonic acid; unsaturated alcohol polyesters of saturated aliphatic and aromatic polycarboxylic acids, e. g., diallyl phthalate, diallyl oxylate, dimethallyl oxylate, diallyl succinate, dimethallyl tartrate; ethers, e. g., divinyl ether, diallyl ether, vinyl allyl ether, dimethallyl ether; and ketones, e. g., divinyl ketone, diallyl ketone, and dimethallyl ketone and their mixtures.

Suitable changes may be made in the details of the process without departing from the spirit or scope of the invention, the proper limits of which are defined in the appended claims.

I claim:

1. An ether-carbonate having the general for mul-a x H o the group consisting of allyl, methallyl, chlor-- allyl, vinyl, methyl, ethyl, butyl and crotyl, at; least one of the substituents being unsaturated,. in which X and Y are monovalent radicals se lect'ed from the-group consisting" of chlorine and; bromine and in which Z isa monova-lentradical from thegroup consisting of chlorine; bromine and.

in which A is a. monovalent, radical selected from the group, consisting of chlorine and bromine and in which'B isa monovalent' radical selected'from the "group consisting of methyl. and" hydrogen.

2. 1-alloXy-2,2;2 trichloroethyl ally carbonate; 3; lj-all'oxy-2;2,3 trichlorobutyl' all'ylcarbonate;

in which Rand R aresubstituents selected from the group consisting of allyl; methallyl, chlorallyl, vinyl, methyl, ethyl; butyland crotyl atleast one ofthe substituents being unsaturated, in which X and Y are monovlalent radicals selected from the group consistingof chlorine and: bromine,- and in which Z is amonovalent radical from the groupconsisting of chlorine, bromineand H. in which A is a inonovalent radical selectedfrom thegroup consisting of chlorine andhromine and in which B is amonovalent radical selected from the groupconsisting of methyl; and. hydrogen 6. The polymer of; 1-al1oxy-2,2,2-trich1oroethyl allyl carbonate.

7. Thepolymer of 1-a11oxy-2,2,3-trichlor0huty1.

allyl carbonate.

8. The polymer of 1-alloxy-2,2,2-trichloroethyl-beta-chlorallyl carbonate.

9.. Themethod of forming an ether-carbonate which comprises reacting acompoundhaving the general formula with; a. chloro-i'ormate having the general forinthe, presence of, an agent capable of'neutralizing hydrogen chlorifde andata temperature between about,.0 andv about 101C:., in which X'and' Y. are monovalent' radicals selected from the cg nsisting of chlorine, bromine. and

B; Y I E' A etawhl m ll l arb na 11. The; polymer of 1 (beta-ch1or all0Xy)-1 ;3= r pblorobn y1r e ae lo oally a e-V are lrallylmcarbonateh HENRY A, PAQE.

HEITE ENQ CI E 40 file of" this: patent:

UNITED STATES PATENTS Numben' Name- Date, 45 1,189,205 Grether et a1. Feb. 6,1943,

321,896; BltittQn-et;;al.. lune. 15,;194fi group consisting, of chlorine and bromine, and in. which Z'Jis'v a monovalentvrad'ical' from the group beta-0 110292 6351 2 r ch b ty V 12- r-be ar hloroal xy ,3 chlor bu r The following references are of record in the 

1. AN ETHER-CARBONATE HAVING THE GENERAL FORMULA 